KR100451005B1 - Preparation of cellulose-based adsorbents containing the quaternary ammonium functional groups and their recycling methods - Google Patents
Preparation of cellulose-based adsorbents containing the quaternary ammonium functional groups and their recycling methods Download PDFInfo
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- KR100451005B1 KR100451005B1 KR10-2001-0069748A KR20010069748A KR100451005B1 KR 100451005 B1 KR100451005 B1 KR 100451005B1 KR 20010069748 A KR20010069748 A KR 20010069748A KR 100451005 B1 KR100451005 B1 KR 100451005B1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
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Abstract
본 발명은 양이온성 기능기를 갖는 셀룰로오스계 흡착제와 이의 재생방법에 관한 것으로서, 더욱 상세하게는 셀룰로오스를 알카리 촉매하에서 에폭사이드, 이소시아네이트, 이소티오시아네이트, 아실 할로, 할로겐 및 안하이드라이드 중에서 선택된 기능기를 두 개 이상 포함하는 화합물로 가교반응시킨 후 양이온성 기능기를 갖는 4급암모늄화합물과 반응시켜 양이온성 셀룰로오스 흡착제를 제조함으로써, 종래 염료의 흡착제에 비해 흡착 속도와 흡착량이 매우 커 폐수처리 공정을 크게 개선할 수 있고 흡착제의 재생이 용이하여 폐기물의 처리에 대한 부담이 적으므로 환경친화적이며 경제적인 양이온성 기능기를 갖는 셀룰로오스계 흡착제와 이의 재생방법에 관한 것이다.The present invention relates to a cellulose-based adsorbent having a cationic functional group and a regeneration method thereof, and more particularly, to a cellulose-based functional group selected from epoxide, isocyanate, isothiocyanate, acyl halo, halogen, and anhydride under alkali catalyst. By cross-linking with a compound containing two or more compounds and reacting with a quaternary ammonium compound having a cationic functional group to prepare a cationic cellulose adsorbent, the adsorption rate and the amount of adsorption are very large compared to the adsorbents of conventional dyes, thereby greatly improving the wastewater treatment process. The present invention relates to a cellulose-based adsorbent having a cationic functional group which is environmentally friendly and economical since it can be easily recycled and has a low burden on waste disposal.
Description
본 발명은 양이온성 기능기를 갖는 셀룰로오스계 흡착제와 이의 재생방법에 관한 것으로서, 더욱 상세하게는 셀룰로오스를 알카리 촉매하에서 에폭사이드, 이소시아네이트, 이소티오시아네이트, 아실 할로, 할로겐 및 안하이드라이드 중에서 선택된 기능기를 두 개 이상 포함하는 화합물로 가교반응시킨 후 양이온성 기능기를 갖는 4급암모늄화합물과 반응시켜 양이온성 셀룰로오스 흡착제를 제조함으로써, 종래 염료의 흡착제에 비해 흡착 속도와 흡착량이 매우 커 폐수처리 공정을 크게 개선할 수 있고 흡착제의 재생이 용이하여 폐기물의 처리에 대한 부담이 적으므로 환경친화적이며 경제적인 양이온성 기능기를 갖는 셀룰로오스계 흡착제와 이의 재생방법에 관한 것이다.The present invention relates to a cellulose-based adsorbent having a cationic functional group and a regeneration method thereof, and more particularly, to a cellulose-based functional group selected from epoxide, isocyanate, isothiocyanate, acyl halo, halogen, and anhydride under alkali catalyst. By cross-linking with a compound containing two or more compounds and reacting with a quaternary ammonium compound having a cationic functional group to prepare a cationic cellulose adsorbent, the adsorption rate and the amount of adsorption are very large compared to the adsorbents of conventional dyes, thereby greatly improving the wastewater treatment process. The present invention relates to a cellulose-based adsorbent having a cationic functional group which is environmentally friendly and economical since it can be easily recycled and has a low burden on waste disposal.
염색 공정 후 필연적으로 발생하는 난분해성 염색폐수는 그 성분이 일반적으로 매우 복잡하여 염료나 매염제 이외에 호제 및 세제류 등이 다량 포함되어 있다. 또한 작업 공정의 가동상황에 따라 수질의 일간 변동이 큰 특징을 가지고 있다. 염색 폐수 중의 오염성분은 일반적으로 분해성이 나쁘며, 특히 폐수 중 염료는 미생물에 대한 독성과 저해성을 가지는 성분이 많다.The hardly degradable dye wastewater which is inevitably generated after the dyeing process is generally very complicated and contains a large amount of auxiliaries and detergents in addition to dyes and mordants. In addition, the daily fluctuations in the water quality are large depending on the operating conditions of the work process. Contaminants in dyeing wastewater are generally poorly degradable, and in particular, dyes in wastewater have many toxic and inhibitory effects on microorganisms.
이러한 염료폐수 처리에는 크게 화학적, 물리적, 생물학적 처리방법과 같은 기초적 처리 공정과 최종 고도처리 등 다양한 방법들이 사용되고 있으나 아직까지 효과적인 폐수 처리 시스템이 확립되지 않고 있는 실정이다.Such dye wastewater treatment is mainly used for a variety of methods, such as basic treatment processes such as chemical, physical, and biological treatment and final advanced treatment, but the effective wastewater treatment system has not yet been established.
그 중 화학적 처리방법은 화학 단위 공정을 이용하는 방법으로, 대표적으로 산화제를 사용하여 오염 물질을 화학적으로 분해시켜 폐수 중의 오염원 농도를 낮추는 산화처리 공정이 있다. 화학약품으로는 과산화수소수 등의 산화제가 주로 사용되며, 최근 오존(ozone, O3) 등이 새롭게 각광받고 있으나 처리 후 유독성 부산물을 생성하는 경우가 있으며, 분해된 후 생성된 물질이 폐수 중에 그대로 존재하므로 화학적 산소요구량(COD) 자체가 크게 낮아지지 않는 단점이 있다.Among them, a chemical treatment method is a method using a chemical unit process, and typically there is an oxidation treatment process that lowers the concentration of pollutant in waste water by chemically decomposing contaminants using an oxidant. As chemicals, oxidants such as hydrogen peroxide solution are mainly used. Recently, ozone (Ozone, O 3 ), etc. are newly spotlighted, but they sometimes generate toxic by-products after treatment, and substances generated after decomposition are present in waste water. Therefore, the chemical oxygen demand (COD) itself has a disadvantage that does not significantly lower.
생물학적 처리방법으로는 폭기조(泡起槽, aeration tank) 내에서 미생물을 이용하여 폐수를 처리하는 방법이 있으며, 이는 시설의 설치공간이 많이 요구되며, 처리 시간이 길고 미생물의 활성 유지를 위한 여러 조건들을 만족해야 하고 계절에 따른 처리능의 변동폭이 크다는 단점이 있다. 또한 산화법을 응용한 화학적 처리방법이나 생물학적 처리방법은 처리 후의 색도 제거가 완전하지 못한 문제점이 있다.As a biological treatment method, there is a method of treating wastewater using microorganisms in an aeration tank, which requires a lot of installation space for the facility, a long processing time and various conditions for maintaining the activity of microorganisms. There is a disadvantage in that they must satisfy the fluctuation of the processing capacity according to the season. In addition, the chemical treatment method or biological treatment method using the oxidation method has a problem that the color removal after treatment is not complete.
한편, 물리적 처리방법에서는 활성탄 흡착법이 널리 사용되고 있으나[Nikolaevsky, R.; Monosov, M.; Monosov, E.; Sharony, E.; Gurevich, D. 미국특허 제5,792,336호 (1998)] 사용한 활성탄의 재생 및 폐기 문제가 뒤따른다.On the other hand, activated carbon adsorption is widely used in physical treatment methods [Nikolaevsky, R .; Monosov, M .; Monosov, E .; Sharony, E .; Gurevich, D. US Pat. No. 5,792,336 (1998)] follows the problem of regeneration and disposal of used activated carbon.
따라서, 최근 산업폐수의 색도 제거 문제가 사회적인 문제로 대두되고 있는 추세를 감안하여 상기와 같은 문제점들을 완전하게 해결하고, 실제로 상업적 이용이 가능한 새로운 흡착제의 개발이 필요한 실정이다.Accordingly, in view of the recent trend of removing the chromaticity of industrial wastewater as a social problem, it is necessary to completely solve the above problems and to develop a new adsorbent that is actually commercially available.
이에, 본 발명자들은 상기한 문제점을 해결하기 위하여 셀룰로오스를 알카리 촉매하에서 에폭사이드, 이소시아네이트, 이소티오시아네이트, 아실 할로, 할로겐 및 안하이드라이드 중에서 선택된 기능기를 두 개 이상 포함하는 화합물로 가교반응시킨 후 양이온성 기능기를 갖는 4급암모늄화합물과 반응시켜 양이온성 셀룰로오스 흡착제를 제조함으로써 본 발명을 완성하였다.Accordingly, the present inventors crosslinked cellulose with a compound containing two or more functional groups selected from epoxide, isocyanate, isothiocyanate, acyl halo, halogen and anhydride under alkali catalyst to solve the above problems. The present invention has been completed by preparing a cationic cellulose adsorbent by reacting with a quaternary ammonium compound having a cationic functional group.
따라서, 본 발명은 염료에 대한 흡착 성능이 우수하고, 흡착 속도와 흡착량이 매우 커 폐수처리 공정을 크게 개선할 수 있고 흡착제의 재생이 용이한 양이온성 기능기를 갖는 셀룰로오스계 흡착제와 이의 재생방법을 제공하는데 그 목적이 있다.Accordingly, the present invention provides a cellulose-based adsorbent having a cationic functional group having excellent adsorption performance for dyes, a large adsorption rate and a large amount of adsorption, which can greatly improve the wastewater treatment process, and easily regenerate the adsorbent, and a method for regenerating the same. Its purpose is to.
본 발명은 셀룰로오스를 알카리 촉매하에서 에폭사이드, 이소시아네이트, 이소티오시아네이트, 아실 할로, 할로겐 및 안하이드라이드 중에서 선택된 기능기를 두 개 이상 포함하는 화합물로 가교반응시킨 후, 4급암모늄화합물과 반응시켜 얻은 양이온성 셀룰로오스 흡착제를 그 특징으로 한다.The present invention is obtained by crosslinking a cellulose with a compound containing two or more functional groups selected from epoxide, isocyanate, isothiocyanate, acyl halo, halogen and anhydride under an alkali catalyst and then reacting with a quaternary ammonium compound. It is characterized by a cationic cellulose adsorbent.
본 발명은 염료가 흡착된 양이온성 셀룰로오스 흡착제를 NaCl, HCl 및 구아니딘 중에서 선택된 것으로 처리하여 흡착제를 재생하는 방법을 또 다른 특징으로 한다.The present invention further features a method of regenerating the adsorbent by treating the dye-adsorbed cationic cellulose adsorbent with one selected from NaCl, HCl and guanidine.
이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 셀룰로오스를 알카리 촉매하에서 에폭사이드, 이소시아네이트, 이소티오시아네이트, 아실 할로, 할로겐 및 안하이드라이드 중에서 선택된 기능기를 두 개 이상 포함하는 화합물로 가교반응시킨 후 양이온성 기능기를 갖는 양이온성 기능기를 갖는 4급암모늄화합물과 반응시켜 얻은 양이온성 셀룰로오스 흡착제와 상기 흡착제를 염료 폐수 처리에 사용한 후 재생하는 방법에 관한 것이다.The present invention crosslinks cellulose with a compound containing two or more functional groups selected from epoxide, isocyanate, isothiocyanate, acyl halo, halogen and anhydride under an alkali catalyst and then cationic functional group having a cationic functional group. It relates to a cationic cellulose adsorbent obtained by reacting with a quaternary ammonium compound having and a method for regenerating the adsorbent after use in dye wastewater treatment.
본 발명에 따른 흡착제의 기반물질로는 천연 고분자의 일종인 셀룰로오스를 사용한다. 상기 셀룰로오스는 50 ∼ 100 μm의 입자 또는 침상 형태의 것을 사용하는 것이 바람직하고, 상기 셀룰로오스에 각종 양이온성 기능기를 도입하기 위해 먼저 셀룰로오스를 가교반응시킨다. 가교반응은 대개 알카리 촉매하에서 양쪽 기능기를 갖는 화합물을 이용하여 반응시키며, 이는 양이온성 기능기가 도입된 셀룰로오스가 물에 녹는 것을 방지하기 위함이다. 또한 가교반응을 통해 흡착제의 기계적인 강도를 확보할 수 있다. 본 발명은 일반적으로 가교반응에 사용되는 화합물인 에폭사이드(epoxide), 이소시아네이트(isocyanate), 이소티오시아네이트(isothiocyanate), 아실 할로(acyl halide), 할로겐(halogen), 안하이드라이드(anhydride) 기능기를 두 개 이상 포함하는 화합물을 사용할 수 있다. 특히, 본 발명은 상기 화합물 중 가장 경제적인 가격으로 쉽게 구할 수 있는 에폭사이드 기능기를 갖는 에피클로로 히드린, 글리세롤디글리시딜에테르 및 폴리에틸렌디글리시딜에테르 중에서 선택된 화합물로 가교반응시키는 것이 좋다. 그리고, 이소시아네이트기를 갖는 화합물로는 헥사메틸렌 디이소시아네이트(Hexamethylene diisocyanate) 류의 지방족 화합물, 톨루엔 2.4-디이소시아네이트(Toluene 2,4-diisocyanate) 류의 방향족 화합물 등을 사용할 수 있으며, 이소티오시아네이트기를 갖는 화합물로는 헥사메틸렌 디이소티오시아네이트(Hexamethylene diisothiocyanate) 류의 지방족 화합물, 톨루엔 2.4-디이소티오시아네이트(Toluene 2,4-diisothiocyanate) 류의 방향족 화합물 등을 사용할 수 있으며, 아실 할로기를 갖는 화합물로는 포스젠(Phosgen), 트리포스젠(Triphosgen) 류의 아실 할로 화합물, 아디포일 클로라이드(Adipoyl chloride) 류의 지방족 화합물, 테레프탈로일 클로라이드(Terephthaloyl chloride) 류의 방향족 화합물 등을 사용할 수 있으며, 할로겐기를 갖는 화합물로는 1.4-디클로로부탄(1,4-Dichlorobutane) 류의 지방족 화합물, α,α'-디클로로-p-자일렌(α,α'-Dichloro-p-xylene) 류의 방향족 화합물 등을 사용할 수 있으며, 안하이드라이드기를 갖는 화합물로는 1,2,4,5-벤젠테트라카르복실릭 디안하이드라이드(1,2,4,5-Benzenetetracarboxylic dianhydride) 류의 방향족 화합물 등을 사용할 수 있다.As the base material of the adsorbent according to the present invention, cellulose which is a kind of natural polymer is used. The cellulose is preferably used in the form of particles of 50-100 μm or in the form of needles, and crosslinking the cellulose first to introduce various cationic functional groups into the cellulose. The crosslinking reaction is usually carried out using a compound having both functional groups under an alkaline catalyst, in order to prevent the cellulose into which the cationic functional group is introduced is dissolved in water. In addition, it is possible to ensure the mechanical strength of the adsorbent through the crosslinking reaction. Epoxide, isocyanate, isothiocyanate, acyl halide, halogen, anhydride function of the compounds generally used in the crosslinking reaction Compounds containing two or more groups can be used. In particular, the present invention is preferably crosslinked with a compound selected from epichlorohydrin, glycerol diglycidyl ether and polyethylene diglycidyl ether having an epoxide functional group which can be easily obtained at the most economical price among the compounds. As the compound having an isocyanate group, an aliphatic compound of hexamethylene diisocyanate or an aromatic compound of toluene 2.4-diisocyanate can be used. As the compound, an aliphatic compound of hexamethylene diisothiocyanate class, an aromatic compound of toluene 2.4-diisothiocyanate class, etc. may be used, and a compound having an acyl halo group. For example, phosgen, triphosgen acyl halo compounds, adipoyl chloride aliphatic compounds, terephthaloyl chloride aromatic compounds, etc. may be used. Examples of the compound having a halogen group include aliphaticization of 1.4-dichlorobutane. Water, an aromatic compound of α, α'-Dichloro-p-xylene, etc. may be used, and the compound having an anhydride group may be 1,2,4,5 Aromatic compounds of the benzenetetracarboxylic dianhydride (1,2,4,5-Benzenetetracarboxylic dianhydride) and the like can be used.
상기 가교반응시 가교도는 약 1 ∼ 50%가 바람직하고, 만일 가교도가 1% 미만인 경우에는 셀룰로오스의 용해를 완전히 방지할 수 없으며, 기계적인 강도가 낮아서 처리공정에서 응용할 수 없다. 또한 가교도가 50%를 초과하는 경우에는 셀룰로오스 기본 골격 사이의 공간이 충분히 확보되지 않아 반응물의 물질 전달이 원활하지 못하게 되며, 이에 따라 기능기 도입 수율이 낮아지는 문제점이 있다. 뿐만 아니라 폐수 안에 존재하는 염료를 흡착할 때에도 이와 같은 물질 전달 문제가 발생하여 흡착능이 저하된다. 그리고, 상기 알칼리 촉매로는 NaOH, KOH, Na2CO3, K2CO3등을 사용할 수 있다.In the crosslinking reaction, the degree of crosslinking is preferably about 1 to 50%. If the degree of crosslinking is less than 1%, the dissolution of cellulose cannot be completely prevented, and the mechanical strength is low, and thus the crosslinking degree is not applicable to the treatment step. In addition, when the degree of crosslinking exceeds 50%, there is a problem in that the space between the cellulose basic skeletons is not sufficiently secured so that mass transfer of the reactants is not smooth, and thus the yield of functional group introduction is lowered. In addition, such a mass transfer problem occurs when the dye is adsorbed in the waste water, thereby decreasing the adsorption capacity. The alkali catalyst may be NaOH, KOH, Na 2 CO 3 , K 2 CO 3, or the like.
다음으로, 상기 가교된 셀룰로오스에 양이온성 기능기를 갖는 4급암모늄화합물을 첨가하여 반응시켜 양이온성 셀룰로오스 흡착제를 제조한다. 본 발명에서는 상기 4급암모늄화합물로 글리시딜 트리메틸암모늄클로라이드 또는 3-클로로-2-히드록시프로필 트리메틸암모늄클로라이드를 사용하는 것이 좋다. 대개 염료폐수에 존재하는 염료는 음이온성 기능기를 가지고 물 속에 용해되어 있는데, 양이온성 셀룰로오스 흡착제의 도입된 양이온성 기능기는 이러한 음이온성의 염료들과 정전기적 인력이 작용하여 흡착능을 보인다. 따라서, 양이온성 반응기의 도입량이 커질수록 흡착능이 증가하는 것을 확인할 수 있다. 그러나, 일정 수준 이상의 기능기 도입량에서는 더 이상의 흡착능 증가가 나타나지 않는데, 이는 흡착제 표면에 염료가 흡착할 수 있는 공간이 포화상태에 이르렀기 때문이다. 상기에서 양이온성 기능기의 함량은 0.2 ∼ 2.0 mmol/g로 반응시키는 것이 바람직하며,만일 그 함량이 0.2 mmol/g 미만이면 폐수에 존재하는 염료에 대한 흡착능이 현저하게 저하되는 문제가 있다.Next, a quaternary ammonium compound having a cationic functional group is added to the cross-linked cellulose to react to prepare a cationic cellulose adsorbent. In the present invention, it is preferable to use glycidyl trimethylammonium chloride or 3-chloro-2-hydroxypropyl trimethylammonium chloride as the quaternary ammonium compound. The dyes present in the dye wastewater are usually dissolved in water with anionic functional groups. The cationic functional groups of cationic cellulose adsorbents exhibit adsorptive capacity due to the action of these anionic dyes and electrostatic attraction. Therefore, it can be seen that the adsorption capacity increases as the introduction amount of the cationic reactor increases. However, the amount of functional groups introduced over a certain level does not show any increase in adsorption capacity, since the space for dye adsorption on the surface of the adsorbent is saturated. In the above, the content of the cationic functional group is preferably reacted at 0.2 to 2.0 mmol / g, and if the content is less than 0.2 mmol / g, there is a problem in that the adsorption capacity for dyes present in the wastewater is significantly lowered.
상기한 본 발명에 따른 양이온성 셀룰로오스 흡착제는 0.01 ∼ 5 mm의 분말형 또는 과립형으로 염색 폐수에 사용하면 폐수 중의 오염원을 빠른 시간 내에 효율적으로 흡착하여 제거할 수 있다.When the cationic cellulose adsorbent according to the present invention is used for dyeing wastewater in a powder form or granule of 0.01 to 5 mm, it is possible to efficiently adsorb and remove the contaminant in the wastewater within a short time.
또한, 본 발명은 상기한 양이온성 셀룰로오스 흡착제를 염색 폐수에 사용하고 난 후 염료가 흡착된 양이온성 셀룰로오스 흡착제를 NaCl, HCl 및 구아니딘 중에서 선택된 것으로 처리하여 흡착제를 재생하는 방법을 포함한다. 염료가 흡착된 양이온성 셀룰로오스 흡착제를 0.1 ∼ 10N 농도의 NaCl, HCl 및 구아니딘 수용액으로 상온에서 일정 시간동안 세척함으로써 재생할 수 있다.The present invention also includes a method of regenerating the adsorbent by using the cationic cellulose adsorbent described above for dyeing wastewater and then treating the cationic cellulose adsorbent to which the dye is adsorbed as selected from NaCl, HCl and guanidine. The dye-adsorbed cationic cellulose adsorbent can be regenerated by washing with a solution of NaCl, HCl and guanidine at a concentration of 0.1-10 N at room temperature for a certain time.
이와 같은 본 발명을 실시예에 의거하여 상세하게 설명하겠는 바, 본 발명이 실시예에 한정되는 것은 아니다.Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.
실시예 1.Example 1.
셀룰로오스(50 μm의 입자 형태) 10.0 g과 NaOH 2.5 g을 반응기에 넣고 증류수 50.0 mL를 가하고 여기에 에피클로로 히드린(Epichlorohydrin) 2.4 mL를 가한 후 가열하면서 가교시켰다. 가교 반응된 셀룰로오스에 글리시딜트리메틸암모니움클로라이드(Glycidyl trimethyl ammonium chloride, GTMAC) 12.0 mL를 가하고 계속 반응시켜 양이온성 셀룰로오스 흡착제를 제조하였다. 반응 후 여과하여 증류수와 메탄올로 세척하고 건조하였다.10.0 g of cellulose (50 μm particles) and 2.5 g of NaOH were added to a reactor, 50.0 mL of distilled water was added thereto, and 2.4 mL of epichlorohydrin was added thereto, followed by crosslinking while heating. 12.0 mL of glycidyl trimethyl ammonium chloride (GTMAC) was added to the cross-linked cellulose, and the reaction was continued to prepare a cationic cellulose adsorbent. After the reaction was filtered, washed with distilled water and methanol and dried.
실시예 2.Example 2.
셀룰로오스(50 μm의 입자 형태) 10.0 g과 NaOH 2.5 g을 반응기에 넣고 증류수 50.0 mL를 가하고 여기에 글리세롤디글리시딜에테르(Glycerol diglycidyl ether) 5.0 mL를 가한 후 가열하면서 가교시켰다. 가교 반응된 셀룰로오스에 GTMAC 12.0 mL를 가하고 계속 반응시켜 양이온성 셀룰로오스 흡착제를 제조하였다. 반응 후 여과하여 증류수와 메탄올로 세척하고 건조하였다.10.0 g of cellulose (50 μm particles) and 2.5 g of NaOH were added to a reactor, 50.0 mL of distilled water was added thereto, and 5.0 mL of glycerol diglycidyl ether was added thereto, followed by crosslinking while heating. 12.0 mL of GTMAC was added to the cross-linked cellulose and the reaction was continued to prepare a cationic cellulose adsorbent. After the reaction was filtered, washed with distilled water and methanol and dried.
실시예 3.Example 3.
셀룰로오스(50 μm의 입자 형태) 10.0 g과 NaOH 2.5 g을 반응기에 넣고 증류수 50.0 mL를 가하고 여기에 폴리에틸렌글리콜디글리시딜에테르(Poly(ethylene glycol) diglycidyl ether) 9.0 g을 가한 후 가열하면서 가교시켰다. 가교 반응된 셀룰로오스에 GTMAC 12.0 mL를 가하고 계속 반응시켜 양이온성 셀룰로오스 흡착제를 제조하였다. 반응 후 여과하여 증류수와 메탄올로 세척하고 건조하였다.10.0 g of cellulose (50 μm particles) and 2.5 g of NaOH were added to a reactor, 50.0 mL of distilled water was added thereto, and 9.0 g of polyethylene (diglycol) diglycidyl ether was added thereto, followed by crosslinking while heating. . 12.0 mL of GTMAC was added to the cross-linked cellulose and the reaction was continued to prepare a cationic cellulose adsorbent. After the reaction was filtered, washed with distilled water and methanol and dried.
실시예 4.Example 4.
셀룰로오스(50 μm의 입자 형태) 10.0 g과 NaOH 2.5 g을 반응기에 넣고 증류수 50.0 mL를 가하고 여기에 에피클로로 히드린(Epichlorohydrin) 2.4 mL를 가한 후 가열하면서 가교시켰다. 가교 반응된 셀룰로오스에 3-클로로-2-히드록시프로필 트리메틸암모늄클로라이드((3-Chloro-2-hydroxy)propyl trimethyl ammonium chloride) 20.0 mL를 가하고 계속 반응시켜 양이온성 셀룰로오스 흡착제를 제조하였다. 반응 후 여과하여 증류수와 메탄올로 세척하고 건조하였다.10.0 g of cellulose (50 μm particles) and 2.5 g of NaOH were added to a reactor, 50.0 mL of distilled water was added thereto, and 2.4 mL of epichlorohydrin was added thereto, followed by crosslinking while heating. 20.0 mL of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride was added to the cross-linked cellulose, and the reaction was continued to prepare a cationic cellulose adsorbent. After the reaction was filtered, washed with distilled water and methanol and dried.
시험예 1.Test Example 1.
실시예 1 ∼ 4에서 제조한 양이온성 셀룰로오스 흡착제 25 mg을 각각 취해 반응기에 넣었다. 여기에 100 mg/L의 농도로 제조한 Congo Red 염료, Reactive Black 5 염료, Reactive Orange 16 염료, Reactive Red 4 염료, Reactive Yellow 2 염료, Reactive Red 2 염료, Re active Blue 19 염료 또는 Reactive Blue 4 염료 용액 50 ml을 각 반응기에 넣고 2시간 후 염료 용액의 흡광도를 UV/VIS 광도계(UV/VIS spectrophotometer)로 측정하였다. 그 결과는 다음 표 1에 나타내었다.25 mg of the cationic cellulose adsorbents prepared in Examples 1 to 4 were each taken and placed in a reactor. Congo Red dye, Reactive Black 5 dye, Reactive Orange 16 dye, Reactive Red 4 dye, Reactive Yellow 2 dye, Reactive Red 2 dye, Reactive Blue 19 dye or Reactive Blue 4 dye 50 ml of the solution was placed in each reactor, and after 2 hours, the absorbance of the dye solution was measured with a UV / VIS spectrophotometer. The results are shown in Table 1 below.
비교예로 종래 흡착제로 사용된 한국 삼천리 카보텍사 야자계 활성탄(비교예 1), 한국 삼천리 카보텍사 석탄계 활성탄(비교예 2), 미국 칼곤사 활성탄 F-300(비교예 3), 미국 칼곤사 활성탄 F-400(비교예 4), 독일 롬 & 하스사 음이온교환수지 앰버라이트 IRA-900(비교예 5), 독일 롬 & 하스사 음이온교환수지 앰버라이트 IRA-67(비교예 6) 및 독일 롬 & 하스사 음이온교환수지 듀올라이트 A-7(비교예 7)를 사용하여 상기와 같은 방법으로 흡광도를 측정하였고, 그 결과를 다음 표 1에 나타내었다.Comparative Examples: Samchully Carbotec Co., Ltd. Coal Activated Carbon (Comparative Example 1), Samchully Cobotec Coal Activated Carbon (Comparative Example 2), Korea Calgonsa Activated Carbon F-300 (Comparative Example 3), USA F-400 (Comparative Example 4), Rom & Haas, Germany Anion Exchange Resin Amberlite IRA-900 (Comparative Example 5), Rom & Haas, Anion Exchange Resin Amberlite IRA-67 (Comparative Example 6), Germany Absorbance was measured in the same manner as above using Haas' anion exchange resin Duolite A-7 (Comparative Example 7), and the results are shown in Table 1 below.
상기 표 1에 나타난 바와 같이, 본 발명에 따른 실시예 1 ∼ 4의 양이온성 셀룰로오스 흡착제를 사용한 경우 종래의 일반적인 무기계(無機係) 흡착제(비교예 1 ∼ 4)나 이온교환수지(비교예 5 ∼ 7)에 비해 염료 제거 효율이 뛰어남을 확인 할 수 있었다.As shown in Table 1 above, in the case of using the cationic cellulose adsorbents of Examples 1 to 4 according to the present invention, conventional inorganic inorganic adsorbents (Comparative Examples 1 to 4) or ion exchange resins (Comparative Examples 5 to 4). Compared with 7), the dye removal efficiency was excellent.
시험예 2.Test Example 2.
시험예 1에서 Reactive Black 5 염료를 흡착한 실시예 1의 양이온성 셀룰로오스 흡착제 12.5 mg을 반응기에 넣고 1N NaCl 25 ml을 가했다. 2시간 후 용액의 흡광도를 UV/VIS 광도계(UV/VIS spectrophotometer)로 측정하였다. 1N NaCl 1회 처리 결과 흡착된 염료의 34.3%가 용액 중으로 용출되었다.In Test Example 1, 12.5 mg of the cationic cellulose adsorbent of Example 1 adsorbed with the Reactive Black 5 dye was placed in a reactor, and 25 ml of 1N NaCl was added. After 2 hours the absorbance of the solution was measured with a UV / VIS spectrophotometer. One treatment with 1N NaCl eluted 34.3% of the adsorbed dye into the solution.
시험예 3.Test Example 3.
시험예 1에서 Reactive Black 5 염료를 흡착한 실시예 1의 양이온성 셀룰로오스 흡착제 12.5 mg을 반응기에 넣고 약 1N HCl 25 ml을 가했다. 2시간 후 용액의 흡광도를 UV/VIS 광도계(UV/VIS spectrophotometer)로 측정하였다. 1N HCl 1회 처리 결과 흡착한 염료의 13.0%가 용액 중으로 용출되었다.In Experiment 1, 12.5 mg of the cationic cellulose adsorbent of Example 1 adsorbed with the Reactive Black 5 dye was placed in a reactor, and 25 ml of about 1N HCl was added thereto. After 2 hours the absorbance of the solution was measured with a UV / VIS spectrophotometer. After 1 N HCl treatment, 13.0% of the adsorbed dye was eluted into the solution.
시험예 4.Test Example 4.
시험예 1에서 Reactive Black 5 염료를 흡착한 실시예 1의 양이온성 셀룰로오스 흡착제 12.5 mg을 반응기에 넣고 약 1M 구아니딘(Guanidine) 25 ml을 가했다. 2시간 후 용액의 흡광도를 UV/VIS 광도계(UV/VIS spectrophotometer)로 측정하였다. 약 1N 구아니딘 1회 처리 결과 흡착한 염료의 78.0%가 용액 중으로 용출되었다.In Test Example 1, 12.5 mg of the cationic cellulose adsorbent of Example 1 adsorbed with the Reactive Black 5 dye was placed in a reactor, and 25 ml of about 1 M Guanidine was added thereto. After 2 hours the absorbance of the solution was measured with a UV / VIS spectrophotometer. One treatment of about 1N guanidine elutes 78.0% of the adsorbed dye into the solution.
시험예 2 ∼ 4의 결과로부터 알수 있는 바와 같이, 염료가 포함된 양이온성셀룰로오스를 NaCl 등의 염 수용액과 HCl 등의 산 수용액 또는 구아니딘과 같은 유기아민 수용액으로 처리하여 흡착제인 양이온성 셀룰로오스를 재생하여 사용할 수 있음을 확인할 수 있었다.As can be seen from the results of Test Examples 2 to 4, the cationic cellulose containing the dye was treated with an aqueous salt solution such as NaCl and an aqueous acid solution such as HCl or an organic amine solution such as guanidine to regenerate the cationic cellulose as an adsorbent. It could be confirmed that it can be used.
상술한 바와 같이, 본 발명에 따른 양이온성 기능기를 갖는 셀룰로오스 흡착제는 종래 염료의 흡착제에 비해 흡착 속도와 흡착량이 매우 커 폐수처리 공정을 크게 개선할 수 있고, 사용한 셀룰로오스 흡착제의 재생이 용이하여 폐기물의 처리에 대한 부담이 적으므로 환경친화적일 뿐만 아니라 경제적인 장점이 있다.As described above, the cellulose adsorbent having a cationic functional group according to the present invention has a very high adsorption rate and amount of adsorption compared to conventional adsorbents of dyes, and can greatly improve the wastewater treatment process. Less burden on processing is not only environmentally friendly but also economically advantageous.
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| JPH10110383A (en) * | 1996-09-30 | 1998-04-28 | Fuji Spinning Co Ltd | Cellulosic fiber product having oil and fat absorbability and antibacterial property, and its production |
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| JPH10110383A (en) * | 1996-09-30 | 1998-04-28 | Fuji Spinning Co Ltd | Cellulosic fiber product having oil and fat absorbability and antibacterial property, and its production |
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